CN110797521A - Silicon-based negative electrode material for lithium ion battery, preparation thereof, negative plate and secondary battery - Google Patents

Silicon-based negative electrode material for lithium ion battery, preparation thereof, negative plate and secondary battery Download PDF

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CN110797521A
CN110797521A CN201911232300.1A CN201911232300A CN110797521A CN 110797521 A CN110797521 A CN 110797521A CN 201911232300 A CN201911232300 A CN 201911232300A CN 110797521 A CN110797521 A CN 110797521A
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silicon
negative electrode
lithium ion
ion battery
lithium
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丁旭丽
梁道伟
赵洪达
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Jiangsu University of Science and Technology
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention discloses a silicon-based negative electrode material for a lithium ion battery, a preparation method thereof, a negative electrode plate and a secondary batteryxM, wherein M is one or more of Fe, Mn, Co, Sn, Ti, Cu and Ni; SiO 2xIn the formula, x is more than or equal to 0 and less than or equal to 2; c: SiO 2x: the molar ratio of M is (0.5-1): (1-5): 1. utilize theThe negative electrode made of the negative electrode composite material shows excellent cycling stability and rate capability, and the conductivity of the composite material is effectively improved.

Description

Silicon-based negative electrode material for lithium ion battery, preparation thereof, negative plate and secondary battery
Technical Field
The invention relates to the technical field of battery preparation, in particular to a silicon-based negative electrode material for a lithium ion battery, preparation thereof, a negative electrode plate and a secondary battery.
Background
Currently, the lithium ion battery cathode materials commercially produced in the market are mainly carbon-based cathode materials, including graphite and mesophase carbon microsphere cathode materials. The theoretical capacity of the cathode material is about 372 mAh/g, actually reaches 370mAh/g, and the capacity of the graphite cathode material is almost not improved. Meanwhile, the preparation process of the carbon cathode material is slightly complicated. Therefore, it is necessary to develop a lithium ion battery cathode material with large theoretical capacity, which can be commercialized and produced in large scale.
In recent years, a variety of novel high-capacity and high-rate anode materials have been developed and put into practical use, and among them, anode materials of silicon type and metal oxide type have been the focus of research. The material is mainly benefited from the characteristics of abundant reserves and high theoretical capacity, the theoretical capacity of silicon is up to 4200 mAh/g, the theoretical capacity of ferric oxide is up to 1007 mAh/g, and other metal oxides such as manganese dioxide, cobaltosic oxide, tin dioxide, titanium dioxide, copper dioxide, nickel oxide and the like also have high capacity. However, both silicon-based materials and metal oxides have respective disadvantages when used as negative electrode materials of lithium ion batteries, such as structural damage caused by large volume deformation caused by intercalation and deintercalation of lithium ions during charge and discharge processes and low conductivity of the materials, and the defects restrict the possibility of further commercial application of the materials.
Patent CN 102208614A discloses a preparation method of carbon-coated ferric oxide as a negative electrode material of a lithium ion battery, the production steps of the compound are complicated, the operability is poor, and especially the hydrothermal reaction is needed to prepare the target product, so that the defects of poor shape controllability, low yield and the like exist, and the compound is not suitable for large-scale commercial production.
Patents CN 103413927A and CN 103618069A disclose a lithium carbonate/ferric oxide composite lithium ion battery cathode material and a preparation method thereof, the theoretical capacity of lithium carbonate itself is quite low, which is only 150-160 mAh/g, so the overall capacity of the composite after the two are combined is still relatively low, and the requirement of a high-performance lithium ion battery cannot be satisfied.
Patent CN 103682251A discloses a porous ferric oxide/carbon nanosheet composite lithium ion battery cathode material and a preparation method thereof, the preparation conditions of the composite are harsh, the composite needs to be subjected to a closed reaction at a high temperature of 1000 ℃ for 10 hours, secondary heating needs to be continued at a temperature of 600 ℃ for 6 hours after the initial reaction is finished, and the complex synthesis process and the harsh preparation conditions greatly improve the preparation cost of the composite and limit the application and popularization of the composite.
Patent CN 102437318A discloses a silicon-carbon composite lithium ion battery cathode material and a preparation method thereof, wherein phenolic resin is coated outside silicon particles, and then the phenolic resin is changed into a coating layer of hard carbon through high-temperature pyrolysis, so as to obtain the silicon-carbon cathode material with a carbon-coated core-shell structure. However, the synthetic process of the phenolic resin has the defects of high toxicity, high cost and the like, and the carbon obtained by pyrolyzing the resin has high hardness and cannot be well adapted to the volume change of silicon. Therefore, the cycle stability of this composite material is relatively poor.
Patent CN 102983317A discloses a silicon-carbon composite lithium ion battery cathode material and a preparation method thereof, which comprises blending silicon particles and a precursor of carbon to obtain a mixed slurry of the silicon particles and the precursor of the carbon, and then carbonizing at high temperature to obtain a silicon-carbon composite. However, the composite obtained by the production process has the defects of nonuniform silicon distribution, easy agglomeration and the like. Meanwhile, the carbonization temperature is high, the process difficulty is high, and the production cost is high.
To date, no composite system with silicon oxide, metal and carbon as a whole has been found to be useful as a negative electrode material for lithium ion batteries.
Disclosure of Invention
Aiming at the problems in the prior art, the invention discloses a silicon-based negative electrode material for a lithium ion battery and a preparation method thereof, and a negative electrode plate and a secondary battery are prepared on the basis of the silicon-based negative electrode material. The negative electrode material is a silicon oxide/metal/carbon composite negative electrode material, and the invention firstly puts two negative electrode materials which are independently researched before silicon oxide and metal into a composite system for research, thereby fully playing the advantages of the silicon oxide and the metal and solving the defects of the silicon oxide and the metal.
The technical scheme of the invention is as follows: a silicon-based negative electrode material for lithium ion batteries is a metal/silicon oxide/carbon composite material C-SiO with a three-dimensional porous structure prepared by a freeze-drying methodxM, wherein M is one or more of Fe, Mn, Co, Sn, Ti, Cu and Ni, SiOxWherein x is more than or equal to 0 and less than or equal to 2, C: SiO 2x: the molar ratio of M is (0.5-1): (1-5): 1.
a preparation method of a silicon-based negative electrode material for a lithium ion battery specifically comprises the following steps:
1) dissolving a carbon source compound and deionized water to obtain a mixed solution A;
2) dissolving a metal source compound and nanoscale silicon oxide in the solution A, and centrifugally stirring for 1-24 h to uniformly dissolve the silicon oxide and the metal source compound in the solution A to obtain a precursor B;
3) and (3) performing freeze drying on the precursor B obtained in the step (2) and then performing high-temperature carbonization to obtain a silicon-based negative electrode material or a mixture C containing the silicon-based negative electrode material.
In step 1, the mixing ratio of the carbon source compound to deionized water is 10 mL H20.5-1 g of carbon source compound is dissolved in O.
In step 2, the weight ratio of the metal source compound to the nanoscale silica is 1: 0.4 to 1: 2.
in step 2, the metal source compound is one or more of an oxide, hydroxide, halide or nitrate compound, soluble organic salt of Fe, Mn, Co, Sn, Ti, Cu or Ni; soluble organic salts include oxalate and acetate salts.
Preferably, the metal source compound is a halide, nitrate or acetate of Fe, Mn, Co, Sn, Ti, Cu or Ni.
In the step 1, the carbon source compound is one or more of citric acid, oleic acid, malic acid, glucose, sucrose, sodium oleate, sodium citrate, sodium malate and polyvinylpyrrolidone.
Preferably, the carbon source compound is glucose or polyvinylpyrrolidone.
In step 2, the nano-sized silica means silica having a particle size of 1 to 1000 nm, preferably 80 to 100 nm.
The negative plate prepared from the negative electrode material further comprises a conductive agent and a binder, wherein the weight percentage range of the negative electrode material is 50-99.5 wt%, the weight percentage range of the conductive agent is 0.1-40 wt%, and the weight percentage range of the binder is 0.1-40 wt%.
The conductive agent is at least one of carbon black, acetylene black, natural graphite, carbon nano tubes, graphene and carbon fibers; the binder is at least one of polytetrafluoroethylene, polyvinylidene fluoride, polyurethane, polyacrylic acid, polyamide, polypropylene, polyvinyl ether, polyimide, styrene-butadiene copolymer and sodium carboxymethylcellulose.
The secondary battery prepared by the negative plate also comprises a positive electrode, a diaphragm and electrolyte.
The positive electrode is a commonly used lithium battery positive electrode, and specifically comprises one of lithium cobaltate, lithium manganate, lithium nickelate, lithium iron phosphate, lithium titanate, a nickel-cobalt-manganese ternary system or a lithium composite metal oxide; the diaphragm comprises one of an aramid diaphragm, a non-woven fabric diaphragm, a polyethylene microporous film, a polypropylene-polyethylene double-layer or three-layer composite film and a ceramic coating diaphragm thereof; the electrolyte comprises an electrolyte and a solvent, wherein the electrolyte is LiPF6、LiBF4、LiClO4、LiAsF6、LiCF3SO3、LiN(CF3SO2) At least one of LiBOB, LiCl, LiBr and LiI; the solvent comprises at least one of Propylene Carbonate (PC), dimethyl carbonate (DMC), Ethyl Methyl Carbonate (EMC), 1, 2-Dimethoxyethane (DME), ethylene carbonate, propylene carbonate, butylene carbonate, diethyl carbonate, methyl propyl carbonate, acetonitrile, ethyl acetate and ethylene sulfite.
The freeze-drying method is to freeze a substance, so that the volume of the substance is almost unchanged, the original structure is maintained, and the concentration phenomenon is not generated. The dried substance is loose and porous and is in a spongy shape, the substance is dissolved quickly and completely after water is added, the original property is almost immediately recovered, the drying process is carried out under vacuum, oxygen is little, and some substances which are easy to oxidize are protected. Meanwhile, in the freeze drying reaction of the metal, the silicon oxide and the carbon source compound, a metal and silicon oxide modified carbon compound can be obtained, so that the defects of silicon oxide in the process of serving as the lithium battery cathode material are effectively overcome, the defects of poor conductivity, serious volume expansion and the like of the silicon-based cathode material are complemented, and the cycle performance and the capacity of the silicon-based cathode material are improved. Therefore, the freeze-drying method is a simple method which can be used for large-scale commercial production, and is beneficial to effective popularization and acceptance of the novel silicon-based negative electrode material in future commercial application.
The invention has the beneficial effects that:
1. according to the invention, silicon oxide, metal and carbon are compounded to form the negative active material by using a freeze drying method, nano silicon oxide particles are uniformly embedded on carbon layers, and nano metal particles are dispersed among the silicon oxide compounded carbon layers, so that a unique three-dimensional porous structure is formed, the defect of poor conductivity of the silicon oxide and the metal is effectively improved by doping carbon, and meanwhile, a space is reserved for the volume change of the silicon oxide and the metal by the three-dimensional porous structure, so that the stability of the structure is ensured.
2. The lithium ion battery assembled by the negative plate prepared by the negative electrode material has excellent cycling stability and rate capability, and the conductivity of the composite material is effectively improved
3. The invention adopts a freeze drying method to complete the preparation of the cathode material, the reaction method is simple and controllable, large-scale production can be realized, and the synthesis process is favorable for controlling the cost and is commercially popularized and applied.
Drawings
FIG. 1 is a graph of a rate capability test of porous carbon and nano tin coated silicon oxide;
FIG. 2 is a graph of a test of the rate capability of silicon oxide;
FIG. 3 is a graph of the cycle performance test of porous carbon and nano-tin coated silica;
FIG. 4 is a graph showing the cycle performance test of silicon oxide.
Detailed Description
The following examples further illustrate the present invention but are not to be construed as limiting the invention. Modifications and substitutions to methods, procedures, or conditions of the invention may be made without departing from the spirit of the invention.
Example 1
1g of glucose was dissolved in 20 mL of deionized water to prepare a solution, and 0.4 g of tin acetate (C) was added to the solution4H6O4Sn), followed by the addition of 0.6 g of diatomaceous earth (80-100 nm), glucose being used as a precursor of carbon in this experiment. And then putting the solution into a centrifugal machine for centrifugal stirring for 10 hours, putting the solution into a freeze dryer for freezing for 2 hours after centrifugal stirring, and then drying for 8 hours. Carbonizing the freeze-dried product at 500 ℃ for 4 h, naturally cooling to room temperature to finally obtain the target product C-SiOx-Sn. Mixing the prepared tin-coated silicon oxide active substance, conductive carbon black and a binder polyvinylidene fluoride according to the weight ratio of 8: 1: 1, preparing a negative electrode slurry by using 1-methyl-2-pyrrolidone as a solvent, coating the negative electrode slurry on a copper foil to prepare a negative electrode sheet, and drying at 50 ℃ overnight. The electrochemical test is carried out by using a CR2025 type button cell, the counter electrode is an analytically pure metal lithium sheet, and the electrolyte is 1M LiPF6Ethylene Carbonate (EC)/diethyl carbonate (DEC) (volume ratio 1: 1) solution, and the battery separator was Celgard-2320 (microporous polypropylene membrane). The cell assembly was performed in a glove box filled with argon.
Example 2
1g of glucose was dissolved in 20 mL of deionized water to prepare a solution, and 0.3 g of tin acetate (C) was added to the solution4H6O4Sn), followed by the addition of 0.7 g of diatomaceous earth (80-100 nm), glucose being used as a precursor of carbon in this experiment. And then putting the solution into a centrifugal machine for centrifugal stirring for 10 hours, putting the solution into a freeze dryer for freezing for 2 hours after centrifugal stirring, and then drying for 8 hours. Carbonizing the freeze-dried product at 500 ℃ for 4 h, naturally cooling to room temperature to finally obtain the target product C-SiOx-Sn. Mixing the prepared tin-coated silicon oxide active substance, conductive carbon black and a binder polyvinylidene fluoride according to the weight ratio of 8: 1: 1, preparing a negative electrode slurry by using 1-methyl-2-pyrrolidone as a solvent, coating the negative electrode slurry on a copper foil to prepare a negative electrode sheet, and drying at 50 ℃ overnight. The electrochemical test is carried out by using a CR2025 type button cell, the counter electrode is an analytically pure metal lithium sheet, and the electrolyte is 1M LiPF6Ethylene Carbonate (EC)/diethyl carbonate (DEC) (volume ratio 1: 1) solution, and the battery separator was Celgard-2320 (microporous polypropylene membrane). The cell assembly was performed in a glove box filled with argon.
The electrochemical rate and cycle performance of the battery prepared in this example were tested (the results are shown in fig. 1 and fig. 3), and the rate and cycle performance of the uncoated silicon oxide were tested under the same conditions (the results are shown in fig. 2 and fig. 4), and it can be seen from the comparison of the test results that the rate performance and cycle performance of the negative electrode of the lithium battery prepared from the porous carbon and the silicon oxide coated with nano tin prepared in this example are significantly improved. At 3.5 Ag-1The multiplying power performance of the C-SiOx-Sn can reach 380 mAhg under the current density-1(higher than the capacity of graphite); while uncoated silica increased to 2.0 Ag at current density-1The capacity of the battery is already attenuated to zero, and meanwhile, the cycle performance test result shows that the specific capacity of the pure silicon oxide cathode can not be kept stable in the whole test cycle, the capacity of the battery is always changed, and the cycle performance (500 circles) of the silicon oxide coated by the nano tin and the porous carbon is obviously superior to the cycle stability of the uncoated silicon oxide battery cathode.
Example 3
1g of glucose was dissolved in 20 mL of deionized water to prepare a solution, and 0.2 g of tin acetate (C) was added to the solution4H6O4Sn), followed by the addition of 0.8 g of diatomaceous earth (80-100 nm), glucose being used as a precursor of carbon in this experiment. And then putting the solution into a centrifugal machine for centrifugal stirring for 10 hours, putting the solution into a freeze dryer for freezing for 2 hours after centrifugal stirring, and then drying for 8 hours. Carbonizing the freeze-dried product at 500 deg.C for 4 h, and naturallyCooling to room temperature to finally obtain the target product C-SiOx-Sn. Mixing the prepared tin-coated silicon oxide active substance, conductive carbon black and a binder polyvinylidene fluoride according to the weight ratio of 8: 1: 1, preparing a negative electrode slurry by using 1-methyl-2-pyrrolidone as a solvent, coating the negative electrode slurry on a copper foil to prepare a negative electrode sheet, and drying at 50 ℃ overnight. The electrochemical test is carried out by using a CR2025 type button cell, the counter electrode is an analytically pure metal lithium sheet, and the electrolyte is 1M LiPF6Ethylene Carbonate (EC)/diethyl carbonate (DEC) (volume ratio 1: 1) solution, and the battery separator was Celgard-2320 (microporous polypropylene membrane). The cell assembly was performed in a glove box filled with argon.
The foregoing illustrates and describes the principles, general features, and advantages of the present invention. However, the above description is only an example of the present invention, the technical features of the present invention are not limited thereto, and any other embodiments that can be obtained by those skilled in the art without departing from the technical solution of the present invention should be covered by the claims of the present invention.

Claims (10)

1. The silicon-based negative electrode material for the lithium ion battery is characterized in that the negative electrode material is a metal/silicon oxide/carbon composite material C-SiO with a three-dimensional porous structure prepared by a freeze-drying methodxM, wherein M is one or more of Fe, Mn, Co, Sn, Ti, Cu and Ni; SiO 2xIn the formula, x is more than or equal to 0 and less than or equal to 2; c: SiO 2x: the molar ratio of M is (0.5-1): (1-5): 1.
2. the preparation method of the silicon-based negative electrode material for the lithium ion battery according to claim 1, which comprises the following steps:
1) dissolving a carbon source compound and deionized water to obtain a mixed solution A;
2) dissolving a metal source compound and nanoscale silicon oxide in the solution A, and centrifugally stirring for 1-24 h to uniformly dissolve the silicon oxide and the metal source compound in the solution A to obtain a precursor B;
3) and (3) performing freeze drying on the precursor B obtained in the step (2) and then performing high-temperature carbonization to obtain a silicon-based negative electrode material or a mixture C containing the silicon-based negative electrode material.
3. The method for preparing a silicon-based anode material for a lithium ion battery according to claim 2, wherein in the step 1, the mixing ratio of the carbon source compound to the deionized water is H/10 mL20.5-1 g of carbon source compound is dissolved in O.
4. The method for preparing a silicon-based anode material for a lithium ion battery according to claim 2, wherein in the step 2, the weight ratio of the metal source compound to the nanoscale silicon oxide is 1: 0.4-1: 2.
5. the method for preparing a silicon-based anode material for a lithium ion battery according to claim 2, wherein in the step 2, the metal source compound is one or more of an oxide, hydroxide, halide or nitrate compound, soluble organic salt of Fe, Mn, Co, Sn, Ti, Cu or Ni.
6. The method for preparing a silicon-based anode material for a lithium ion battery as claimed in claim 2, wherein in step 1, the carbon source compound is one or more of citric acid, oleic acid, malic acid, glucose, sucrose, sodium oleate, sodium citrate, sodium malate and polyvinylpyrrolidone.
7. The method for preparing a silicon-based negative electrode material for a lithium ion battery according to claim 2, wherein in the step 2, the nano-scale silicon oxide refers to a silicon oxide material with a particle size of 80-100 nm.
8. The negative plate prepared from the silicon-based negative electrode material for the lithium ion battery as claimed in any one of claims 1 to 7, wherein the negative electrode preparation material further comprises a conductive agent and a binder, the weight percentage of the negative electrode material is 50 to 99.5wt%, the weight percentage of the conductive agent is 0.1 to 40wt%, and the weight percentage of the binder is 0.1 to 40 wt%; the conductive agent is at least one of carbon black, acetylene black, natural graphite, carbon nano tubes, graphene and carbon fibers; the binder is at least one of polytetrafluoroethylene, polyvinylidene fluoride, polyurethane, polyacrylic acid, polyamide, polypropylene, polyvinyl ether, polyimide, styrene-butadiene copolymer and sodium carboxymethylcellulose.
9. The secondary battery prepared from the negative electrode sheet according to claim 8, wherein the secondary battery preparation material further comprises a positive electrode, a separator and an electrolyte.
10. The secondary battery according to claim 9, wherein the positive electrode is a commonly used lithium battery positive electrode, and specifically comprises one of lithium cobaltate, lithium manganate, lithium nickelate, lithium iron phosphate, lithium titanate, nickel-cobalt-manganese ternary system, or lithium composite metal oxide; the diaphragm comprises one of an aramid diaphragm, a non-woven fabric diaphragm, a polyethylene microporous film, a polypropylene-polyethylene double-layer or three-layer composite film and a ceramic coating diaphragm thereof; the electrolyte comprises an electrolyte and a solvent, wherein the electrolyte is LiPF6、LiBF4、LiClO4、LiAsF6、LiCF3SO3、LiN(CF3SO2) At least one of LiBOB, LiCl, LiBr and LiI; the solvent comprises at least one of Propylene Carbonate (PC), dimethyl carbonate (DMC), Ethyl Methyl Carbonate (EMC), 1, 2-Dimethoxyethane (DME), ethylene carbonate, propylene carbonate, butylene carbonate, diethyl carbonate, methyl propyl carbonate, acetonitrile, ethyl acetate and ethylene sulfite.
CN201911232300.1A 2019-12-05 2019-12-05 Silicon-based negative electrode material for lithium ion battery, preparation thereof, negative plate and secondary battery Withdrawn CN110797521A (en)

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CN111697219A (en) * 2020-06-30 2020-09-22 深圳市金牌新能源科技有限责任公司 Silicon-carbon composite material, preparation method thereof, negative electrode and application thereof
CN111952569A (en) * 2020-08-20 2020-11-17 江苏科技大学 Silicon oxide-based negative electrode material for lithium ion battery and preparation method thereof
CN113346056A (en) * 2021-05-17 2021-09-03 武汉科技大学 Silicon oxide @ iron oxide/carbon composite lithium ion battery anode material and preparation method thereof
CN113629228A (en) * 2021-07-23 2021-11-09 江苏科技大学 Silicon oxide/phosphide carbonized compound and preparation method and application thereof
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CN114709386A (en) * 2022-03-24 2022-07-05 华南理工大学 Porous silicon-carbon composite material and preparation method and application thereof
CN115304052A (en) * 2022-10-13 2022-11-08 溧阳天目先导电池材料科技有限公司 Wood-based composite hard carbon negative electrode material and preparation method and application thereof
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* Cited by examiner, † Cited by third party
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CN111446440B (en) * 2020-05-22 2022-07-05 扬州大学 Nitrogen-doped carbon-coated hollow mesoporous silica/cobalt nano composite material and lithium ion battery cathode material thereof
CN111697219A (en) * 2020-06-30 2020-09-22 深圳市金牌新能源科技有限责任公司 Silicon-carbon composite material, preparation method thereof, negative electrode and application thereof
CN111952569A (en) * 2020-08-20 2020-11-17 江苏科技大学 Silicon oxide-based negative electrode material for lithium ion battery and preparation method thereof
CN113346056A (en) * 2021-05-17 2021-09-03 武汉科技大学 Silicon oxide @ iron oxide/carbon composite lithium ion battery anode material and preparation method thereof
CN113629228A (en) * 2021-07-23 2021-11-09 江苏科技大学 Silicon oxide/phosphide carbonized compound and preparation method and application thereof
CN113629228B (en) * 2021-07-23 2022-07-22 江苏科技大学 Silicon oxide/phosphide carbonized compound and preparation method and application thereof
CN113725436A (en) * 2021-08-31 2021-11-30 江苏科技大学 Phosphorus-based composite material and preparation method thereof, sodium ion secondary battery cathode and secondary battery
CN114709386A (en) * 2022-03-24 2022-07-05 华南理工大学 Porous silicon-carbon composite material and preparation method and application thereof
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CN116705989A (en) * 2023-07-31 2023-09-05 山东硅纳新材料科技有限公司 Flexible polymer electrolyte silicon integrated electrode and preparation method and application thereof
CN116705989B (en) * 2023-07-31 2023-10-24 山东硅纳新材料科技有限公司 Flexible polymer electrolyte silicon integrated electrode and preparation method and application thereof

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Application publication date: 20200214